Electrochemical and in situ FTIR Spectroscopic Studies of CO2Reduction on Polycrystalline Rh Surface

Abstract

Abstract: The reduction of carbon dioxide on polycrystalline Rh electrode is studied by using programmed potential sweep method and in situ FTIR spectroscopy. Emphases are laid on the study of surface processes involved in the reduction. The adsorbed species derived from CO₂reduction (r-CO₂) have been determined by in situ FTIR as bridge(CO_B) and linear(COL) bonded CO, which yield IRabsorption bands respectively around 1905 and 2020cm^-1. The onset potential of CO₂reduction has been determined at -0.05 V. The programmed potential sweep experiments demonstrated that the oxidation of r-CO₂occurred in a current peak at about 0.36 V, from which the charge of r-CO₂oxidation(Q_ox) has been measured quantitatively. It has been revealed that the Q_oxvaries with the potential(E_r) and the time(t_r) applied for CO₂reduction. At a given t_r, Q_oxincreases along with the decrease of E_rfrom -0.15 V to -0.40 V. At each E_r, Q_oxreaches its saturation value (Q_ox^s) when t_ris longer than 250s. In comparison with the oxidation charge(498μCcm^-2) for a saturation adsorption of CO on Rh electrode, the small value of Qsox(e.g., 270 Ccm^-2even for E_rat -0.40 V) indicates that the quantity of adsorbed CO species produced in CO₂reduction is far from that of a monolayer coverage. The ratio of the intensity of IRband of bridge bonded COto that of linear bonded CO is served to figure out the surface site occupancy by r-CO_2.In considering that the number of surface site occupied by bridge and linear bonded CO is 2 and 1 respectively, the surface site occupancy by r-CO₂has been evaluated at only 73% for CO₂reduction at -0.25V for 600 s. It has been demonstrated that the subsequent adsorption of COon the 27% vacancy surface sites yields mainly linear bonded COspecies, implying that the reduction of a CO₂molecule may need the assistance of a few adjacent surface sites. The in situ FTIRresults also confirmed that the submonolayer of r-CO₂is in a uniform distribution over Rh electrode surface. Finally, a reduction mechanism of CO₂on Rh electrode has been proposed based on results of both programmed potential sweep method and in situ FTIR spectroscopy, in which the hydrogen adsorption is considered as an important step assisting the reduction.

Key words: Rh electrode, CO₂, Electrocatalytic reduction, in situ FTIR spectroscopy, Programmed potential sweep method

CLC Number:

O646.54

TrendMD:

HONG Shuang-Jin, ZHOU Zhi-You, SUN Shi-Gang, SHAO Guo-Qiang, QU Ze-Tang. Electrochemical and in situ FTIR Spectroscopic Studies of CO₂Reduction on Polycrystalline Rh Surface[J]. Chem. J. Chinese Universities, 1999, 20(6): 923.

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Electrochemical and in situ FTIR Spectroscopic Studies of CO₂Reduction on Polycrystalline Rh Surface

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